Azo dyestuffs and process of making same



Patented Jan. 11, 1927.

UNITED \STA HERMANN, WAGNER, WERNER LANG-BEIN, AND KARL BECK, OFHOCHST-ON-THE- MAIN, AND KARL THIESS, OF SINDLINGEN, NEARHOCHST-ON-THE-MAIN, GER- TMANY, ASSIGNORS, BY MESNE ASSIGNMENTS, TOGRASSELL'I DYES'IUFF COR- PORATION, OF NEW YORK,- N. Y., CORPORATION OFDELAWARE.

AZO DYESTUEFS AND PROCESS MAKING SAME.

' No Drawing. Application filed January 29, 1925, Serial No. 5,621, andin Germany February 8, 1924.

stufi's, varying in color from red to violet to black of excellentfastness to light and agood fastness to kier-boiling, are obtained bycansing the diazo-compounds of aromatic amines to act upon productsresulting from the con densation of monoor diamino-carbazols or theirhomologues and substitution products with one or two molecularroportions of ,8- hydroxynaphthoic acid {and its substitution productsin which the ortho position to the hydroxyl group is unoccupied. The azodyestuffs thus obtained can be produced both in substance or on asubstatum, for instance for manufacturing color lakes, and also on thefibre in the manner in which the so-called ice-colors are produced.

The'preparation of the carbazylamides of the B-hydroxynaphthoic acid iscarried out by the samemethod' as that used for the.

preparation of the known fl-hydroxynaphthoic acid arylides. I Thefollowing examples illustrate our invention: J Y

1. 13,8 parts of p-nitraniline are diazotized with 36 parts of.hydrochloric acid of B., and 7 parts of nitrite and the mass is run,while cooling, into a solution of 35,2 parts of the condensation productfrom 18,8 parts of ,8-hydroxynaphthoic acid and 18,2 parts ofamino-carbazol of the following formula:

,NH. (Q49 in 14 parts of caustic soda and 3000 parts of water. Theseparation of the red dyestufi' sets in at once. 'The product is thenstirred for some time and the resulting product filtered and dried.

2. 18,4 parts of benzidinc are diazotized with 60 parts of hydrochloricacid of 20 Be. and 14 parts ofnitrite and the resulting -diazo compoundis run, while cooling, into a solution of 92 partsof the condensationproduct from "37'-,6 artsof-fihydroxynaphthoic acid' and 5 ,8 parts of3-amino-6- Br. 'N-ethylcarbazol in 24 parts of caustic soda and 8000parts of water. Separation of the violet dyestufit' sets in at once. Theresultin product is stirred for some time and then filtered and dried.

3. Groumling': condensation product from 1 molecule of,B-hydroxynaphthoic acid with 1 molecule of 3-aminocarbazolg 13.5 gramsof this product are dissolved in 40 ccm. of caustic soda solution of 34B13. and 30 com. of sodium Turkey-red oil of per cent strength and thesolution is made up with hot water to 1 litre.

Dyeing in a solution of:

2,62 grams of 1-amino-benzene-4 (1-azo- 4'-aminonaphthalene), 5,20 ccm.of hydrochloric acid of 22 B., 1,44 grams of nitrite filled up tol'litre with hot water and neutralized with 4 grams of sodium acetate.

4. Grounding: condensation product from 2 molecules ofB-hydroxynaphthoic acid with 1 molecule of 3.6-diaminocarbazol.

10,2 grams of this product are dissolved in 30 ccm. of caustic soda lyeof 34B. and 30 com. of sodium Turkey-red oil 0t 50 per cent strength andthe solution is made up with hot water to 1 litre.

Dyeing in a solution of:

2,62 grams of 1-amino-benzene-4 (1'-azo 4-aminonaphthalene), 5,2 ccm. ofhydrochloric acid of 22 B., 1,44 grams of nitrite filled up with hotwater to 1 litre and neutralized with 4 grams of sodium acetate.

5. Grounding: condensation product from 1 molecule of,B-hydroxynaphthoic acid with 1 molecule of 3-aminocarbazol.

7 grams of this product are dissolved in 20 com. of caustic sodasolution of 34 B., 15 grams of sodium Turkey-red oil of 50 per centstrength and the solution s made up with hot water to litre.

Dyeing in the following diazo solution 2,91 grams of l-ethoxybenzene-2(1-azo- 4'-a'minonaphthalene) 2,6 ccm. of hydrochloric acid of 22 B.,0,7 2 grams of nitrite filled up with hot water to 1 litre andneutralized with 2 grams of sodium acetate.

6. Grounding: same as specified in Example 5, the dyeing being-performedin a tralized with 2 grams of sodium acetate.

According to Examples 3 to 6 the boiled,

'and then dried cotton yarn is well impreg- In this way deep blackshades of excel lent properties as to fastness are obtained.

By the term diazo compound we understand throughout the specificationand claims not only compounds possessing one diazogroup, but also thosecontainingtwo or more of these pounds.

We claim: I 1. Process of producing azo-dyestufls, congroups, forinstance tetrazo comsisting in combining diazo-compounds' withcondensation products of ,"2-hydroxynaphthalene-3-carboxylic acid andamino carbazols.

2. Process of producing az o-dyestufi's consisting in combiningdiazo-compounds with the condensation product ofQ-hydroxynaphthalene-3-ca'rboxylic acid and 3-amino-carobtainable bycombining the tetra zo-compound of-1-aminobenzene-p-(1-azo-4'-aminonaphthalene) with the condensationprodnot of 2-hydroxynaphthaleue-3-carboxylic acid and 3-amino-carbazol,being a black powder, insoluble in water,soluble in concehtratedsulfuric acid' with a red to blue color, giving black tints of very goodfastness when produced on the vegetable fibre.

, 11. As ,new products, textile materials dyed with the coloring mattersdefined in claim 6.

12. As new products, textile materials dyed with the coloring mattersdefined in Claim 7\ i i i i sisting in combining the tetrazo-compound ofl-amino-benzene-p- (1-azo-4-aminonaphthalene) with the condensationproduct of 2-hydroxy-naphthalene-3-carboxylic acid and 3-amino-carbazol.

6. As-new products, the coloring matters obtainable by combiningdiazo-compounds with condensation products of2-hydroxynaphthalene-3-carboxylic acid and amino carbazols being red toblue to black powders, insoluble in water, soluble in concentratedsulfuric acid with "a red to blue color. 7. As new products, thecoloring matters obtainable by combining diazo-compounds with thecondensation product of Q-hydroxynaphthalene-3-carboxylic acid and3-aminocarbazol, being red to blue to black powders, insoluble in water,soluble in, concentrated sulfuric acid with a red to'blue color.

8. Asnew products, the coloring matters obtainable by combiningdiazo-compounds with the condensation product of one molecule ofQ-hydroxyiiaphthalene-3-carboxylic acid and one molecule of3-amino-carbazol, being red to blue to black powders, insolublein.water, soluble in concentrated sulfuric acid with a red to bluecolor.

9. As new products, the coloring matters obtainable by combining thetetrazo-compound of l-aminobenzene -p-(1'-azo-4-aminonaphthalene) withcondensation'products of 2-hydroxynaphthalene-3-carboxylic acid 1 -andammo-carbazols, being black powders.

insoluble in water, soluble in concentrated sulfuric acid with a red toblue color, giving black tints of very goodfastness when produced on thevegetable fibre.

10. As a new product, the coloring matter of the following formula:

' n I. N I.

C: I nlv 15. As new products, textile materials dyed with the coloringmatter defined in claim 10.

In testimony whereof, we afiix our signatures.

' HERMANN WAGNER. WERNER LANGBEIN. KARL BECK.

KARL THIESS.

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